1. © 2014 Carl Lund, all rights reserved A First Course on Kinetics and Reaction Engineering Class 25

2. Where We’re Going Part I - Chemical Reactions Part II - Chemical Reaction Kinetics Part III - Chemical Reaction Engineering ‣ A. Ideal Reactors ‣ B. Perfectly Mixed Batch Reactors ‣ C. Continuous Flow Stirred Tank Reactors ‣ D. Plug Flow Reactors  25. Reaction Engineering of PFRs  26. Analysis of Steady State PFRs  27. Analysis of Transient PFRs ‣ E. Matching Reactors to Reactions Part IV - Non-Ideal Reactions and Reactors

3. PFR Characteristics Environmental variables change along length of reactor Heat transfer area is limited to the reactor wall Area to Volume is more limited than a CSTR ‣ Can’t add a coil inside the fluid Only option for increasing area is to use smaller diameter tube ‣ Eventually leads to large pressure drop through reactor Sometimes can break reactor into segments with some form of heating/cooling between them Heat/Cool Here

4. PFR Advantages & Disadvantages Distinguishing Features ‣ No agitation  Equally well-suited to gases and liquids  Preferred if a solid catalyst is being used because less abrasion ‣ Reactant concentration decreases continually and product concentration increases continually from inlet to outlet ‣ Temperature may vary over the length of the reactor Preferred Uses ‣ Reactions that require a solid catalyst ‣ Large quantities of reactant to be processed ‣ Reactions that will be run adiabatically or with little heating/cooling ‣ Reactions with “typical” kinetics  High rate or selectivity is favored by high reactant concentration and low product concentration  Same kinds of reactions as are favored in a batch reactor ‣ Reversible reactions

5. Analogy between Batch Reactors and PFRs Fluid element within a PFR is like a batch reactor ‣ perfectly mixed radially ‣ differentially thick so negligible axial differences ‣ no fluid enters the element or leaves it during process Starts reacting when fluid element enters the reactor and stops when it leaves ‣ processing time is equal to the residence time (space time) Qualitatively, PFR performance as a function of space time is the same as the qualitative performance of a batch reactor as a function of processing time dz

6. Questions?

7. Activity 25.1 Suppose reaction (1) and reaction (2) are typical irreversible reactions and further assume that they have exactly the same rate expression (same reaction orders, same pre-exponential factor and same activation energy). In fact, the only difference between them is that reaction (1) is exothermic and reaction (2) is endothermic. Make a single graph showing conversion of A versus space time, and on that graph sketch what the plot would look like (a) for reaction (1) taking place in an adiabatic PFR, (b) for reaction (1) taking place in an isothermal PFR, (c) reaction (2) taking place in an adiabatic PFR and (d) reaction (2) taking place in an isothermal PFR. For each plot explain why it has the shape it does, and then explain why the plots differ from each other in the way they do. A → B(1) A → C(2)

8. Key Features to Determine For each curve ‣ Initial value ‣ Initial slope ‣ Initial curvature  Can it persist? ‣ Competing effects  Minimum, maximum or inflection point ‣ Asymptotic final value Comparing curves ‣ Always above, always below or cross at some point

9. Analysis Isothermal systems will be identical because kinetics are the same ‣ Start at zero conversion  No reaction before entering reactor ‣ Positive slope  High reactant concentration, high rate, reactant consumed, conversion increases ‣ Concave down  Farther into the reactor, reactant concentration smaller, rate smaller, not as much conversion ‣ Asymptotically approaches 100% conversion  At which point slope equals zero Adiabatic systems will differ due to temperature effects ‣ Endothermic reaction, as conversion increases, temperature decreases, rate decreases beyond decrease seen in isothermal ‣ Same shape as isothermal, but always below isothermal curve

10. Adiabatic Exothermic Analysis Competing effects ‣ As conversion increases with space time  reactant concentration decreases tending to decrease rate  temperature increases tending to increase rate ‣ Initially expect temperature effect to predominate leading to concave upward shape ‣ Eventually concentration must predominate  Inflection at point where two effects become equal  Concave down beyond that point Adiabatic exothermic system always above other curves

11. Activity 25.2 The objectives of this activity are ‣ Identify two different types of transient responses to a step change in a PFR operating parameter ‣ Understand what feature of the step change leads to each type of transient response ‣ Examine the duration of the response of a PFR to a step change in one of its operating parameters We will use the PFR shown above in a series of thought experiments to qualitatively probe the transient response of a PFR to a set of step changes in operating parameters ‣ At the instant shown, the step change has just occurred ‣ The green and blue fluid elements are both inside the reactor  The green fluid element is the last one to have entered before the step change  The blue fluid element entered just before the green one ‣ The red and yellow fluid element are both outside the reactor  The yellow fluid element will be the first one to enter after the step change  The red fluid element will enter right after the yellow one

12. Duration of the Transient There was some unspecified step change right after the green fluid element entered the reactor Will the changes that occur in the red fluid element as it moves through the reactor be exactly the same as the changes that occur in the yellow fluid element as it moves through the reactor? ‣ Why or why not? Once the yellow fluid element has reached the outlet from the reactor, will the changes that occur in the next fluid element to enter the reactor as it moves through the reactor be exactly the same as the changes that occur in the yellow fluid element as it moved through the reactor? ‣ Is there a name for this condition On the basis of your answers, can you state how long the transient lasted?

13. Duration of the Transient There was some unspecified step change right after the green fluid element entered the reactor Will the changes that occur in the red fluid element as it moves through the reactor be exactly the same as the changes that occur in the yellow fluid element as it moves through the reactor? Yes, they will be equal ‣ They start at equal compositions, flow at equal rates and experience the same heat transfer with the walls, so there is no difference between them Once the yellow fluid element has reached the outlet from the reactor, will the changes that occur in the next fluid element to enter the reactor as it moves through the reactor be exactly the same as the changes that occur in the yellow fluid element as it moved through the reactor? Yes, they will be equal ‣ The reasons are the same; note every fluid element now has the same experience; the reactor is at steady state On the basis of your answers, can you state how long the transient lasted? ‣ The duration of the transient is the amount of time it takes for the yellow fluid element to reach the reactor outlet, and that is equal to the residence time

14. First Step Change There was a step change in the inlet composition As the green fluid element moves through the reactor, will it experience the exact same changes that the blue element experiences? ‣ Why or why not? As the yellow fluid element moves through the reactor, will it experience the exact same changes that the green fluid element experiences? ‣ Why or why not? As the red fluid element moves through the reactor, will it experience the exact same changes that the yellow fluid element experiences? ‣ Why or why not? What would change if there was a step change in the inlet temperature

15. First Step Change There was a step change in the inlet composition As the green fluid element moves through the reactor, will it experience the exact same changes that the blue element experiences? Yes, they will be equal ‣ They started at equal compositions, flow at equal rates and experience the same heat transfer with the walls, so there is no difference between them As the yellow fluid element moves through the reactor, will it experience the exact same changes that the green fluid element experiences? No, they will be different ‣ The yellow fluid element will be reacting at a different rate than the green due to the composition difference As the red fluid element moves through the reactor, will it experience the exact same changes that the yellow fluid element experiences? Yes, they will be equal ‣ For the same reason that the blue and green elements are equal What would change if there was a step change in the inlet temperature ‣ Again, the blue and the green would be equal; the yellow and red would be equal, but the yellow and green would be different.

16. First Step Change Based on the answers you gave on the previous slide, describe what changes you would observe as a function of time if you observed at the point indicated

17. First Step Change Based on the answers you gave on the previous slide, describe what changes you would observe as a function of time if you observed at the point indicated ‣ There would be no changes over time until the yellow fluid element reached the observation point ‣ When the yellow fluid element reached the observation point, a step change would be observed ‣ After the yellow fluid element had reached the observation point, there would be no more changes over time

18. A Different Kind of Step Change There was a step change increase in the flow rate As the green fluid element moves through the reactor, will it experience the exact same changes that the blue element experiences? ‣ Why or why not? As the yellow fluid element moves through the reactor, will it experience the exact same changes that the green fluid element experiences? ‣ Why or why not? As the red fluid element moves through the reactor, will it experience the exact same changes that the yellow fluid element experiences? ‣ Why or why not? Suppose instead of the flow rate, the temperature of the reactor wall changed (causing a step change in the heat transfer term)?

19. A Different Kind of Step Change There was a step change increase in the flow rate As the green fluid element moves through the reactor, will it experience the exact same changes that the blue element experiences? No, they will be different ‣ When the green element reaches the place where the blue element is, it will not have been in the reactor for as long (due to faster flow), so it will not have reacted as much As the yellow fluid element moves through the reactor, will it experience the exact same changes that the green fluid element experiences? No, they will be different ‣ The reason is the same As the red fluid element moves through the reactor, will it experience the exact same changes that the yellow fluid element experiences? Yes, they will be equal ‣ They enter at equal compositions, flow at equal rates and experience the same heat transfer with the walls, so there is no difference between them Suppose instead of the flow rate, the temperature of the reactor wall changed (causing a step change in the heat transfer term)? Same answers

20. Second Step Change Based on the answers you gave on the previous slide, describe what changes you would observe as a function of time if you observed at the point indicated Compare and contrast the nature of the transient for the preceding case to this case

21. Second Step Change Based on the answers you gave on the previous slide, describe what changes you would observe as a function of time if you observed at the point indicated ‣ As soon as the step change was applied, changes would be observed continually until the yellow fluid element reached the observation point ‣ After the yellow fluid element had reached the observation point, there would be no more changes over time Compare and contrast the nature of the transient for the preceding case to this case ‣ In the first case, there will be a step change that moves along the reactor; it will be located at the interface between the green and yellow fluid elements  This is sometimes referred to as a “front” moving through the reactor ‣ In the second case, there will initially be changes along the whole length of the reactor; as the yellow fluid element moves through, there will be continual changes in front of it, but there will be no changes (at a fixed position) behind it

22. Where We’re Going Part I - Chemical Reactions Part II - Chemical Reaction Kinetics Part III - Chemical Reaction Engineering ‣ A. Ideal Reactors ‣ B. Perfectly Mixed Batch Reactors ‣ C. Continuous Flow Stirred Tank Reactors ‣ D. Plug Flow Reactors  25. Reaction Engineering of PFRs  26. Analysis of Steady State PFRs  27. Analysis of Transient PFRs ‣ E. Matching Reactors to Reactions Part IV - Non-Ideal Reactions and Reactors